Direct dyes, process, and product



Patented Nov. 22, I938 ammo nmho'r urns, rnocnss, Aim monuc'r Swanie s. mossander, Wilmington, Del, assignor to E. I. du Pont de Nemours & Company, Wilmington, DeL, a corporation of Delaware No Drawing. Application June 11,1937.

Serial No. 147,699

J' imam.

dyes of outstanding properties. 1 15 go by the name of cellulose together with the regenerated celluloses, the direct colors which are described inm'y copending application, Serial No. 147,698, azotizing the free amino groups of those colors on the fiber and coupling the colors to suitable cndcomponents. -In the preferred form of.

the invention the direct dye has the formula:

naphthol, and in which the amino group is one of the position consisting of meta or para to the @OHN group, amino-naphthol-sulfonic acid is t-amino--naphthol-7-suifonic' acid. and in which the diamino-diphenyl-urea' is one of the group consisting of 3:3 and 4:4' -dlamino diphenyl-urea.

1D). The direct dyes are prepared by aaotizing and coupg di-(amino-aryD-urea. with N- (no-aroyi) it o-naphthol sulfonic acids or llt-io-aroyl) it ,(ao aroylli enaphthol soiionic, acids.- file aryl oi the diam component is preferably a single benzene nucleus, hut it may also he a single naphthalene nucleus. Aryl may bother substituent groups, such. as

scarlet azo C. The objects of this invention have been 220- complished by applying to cellulose, by which term are included the normal substances which sulfonic acid, and the end component is beta (Cl. H6)

halogen, alkyl, alkoxy, 'alphyl, carboxy, and sulfonic acid. The coupling components to which a the said azotized ureas are coupled may desirably be .N (amino aroyl) amino-naphthoi-sulfonic acids in which the (amino-aroyl) group may be 5 repeated and the amino-aroyl itself may desirably include para-amino-benzoyi-J-acid, meta.-

amino-benzoyl-J-acid, para-amino-benzol-paraamino-benzoyl-J-acid, or meta-amino-benzoylmeta-amino-benaoyl-J-acid. The amino naph- 10 thol sulfonic acid is preferably 2-amino-5- naphthol-7-su1fonic acid, but the isomers thereof and polysulfonic acids (such as l-amino-S-naphthol-3z6-disulfonic acid) may likewise be used.

Y E. The substituents halogen, alkyl, alkoxy, etc.,

may be substituted in any position of the nuclei of these dyes except that the coupling positions in the naphthalene and other nuclei must not be blocked. Y F. In the preferred embodiment'the urea derivative is 3:3'-diamino-diphenyl-urea, but the other ureas such as 4:4'-diamino-diphenyl-urea also produce excellent colors. The dyes will n I usually be applied in the form or their sodium salt.

.G. The following examples illustrate the invention but are not limitative thereof:

' Example I Five parts of cotton piece goods are dyed in the usual manner, known to those in the art, with two hundredths parts of 3:3 -diamino diphenyl urea3(MAB J-acidh. The dyed fabric is rinsed in cold water and put in 200 parts of water at 20 C. Add three tenths parts of sodium nitrite and four tenths parts of sulfuric acid. Stir l5 utes. e with cold Water. Dissolve one tenth part of beta naphthol 200 parts water and one twentieth part of caustic soda. Stir the solution rapidly while ad the above rinsed piece goods. Stir for it minutes. R in cold 2 2,13 water and dry. The dyeing is a scarlet shade. The probable formula of the dye on the fiber is:

J. An advantage of the invention is the production of scarlet and red shade dyeswhich are extremely fast to washing.

HO N: Na|S NHCO 0010; s can N=N OH N=N ONHCONH n H Shade on cotton or Ex. Diazo component Coupling component filmerated celose Beta naphthol Scarlet. 2 3:3'-diam1no-diphenyl urea l-phenyl-3-methyl-5- Yellow scarlet.

lm sitlfiime Do. 3 3 3 d1 m h I Meta-tolylena diam inc. Scarlet.

amino peny urea I ,3 (MAB Lama): Beta naphthol Do. A 3:3-diamino-diphenyl urea one mole PAB J-acid .do D0. 4 rd one male AhlABl J-acid 5 iamino ip eny urea 3 (PAB J-acid). 6 4:4'-diamino-diphenylurea 3 (MAB J-acid); 7 4:4-diamino-diphenylurea one mole PAB J-acid ..do Do. 8 )d one mogle lgAB1 J-acid 3:3'- iamino lp any-urea l 3 (PAB-PAB J-acid), 3z3-diamino-diphenyl-uraa 3 (MAB-MAB J-acid);

H. The preferred end compound is beta-naphthol, but 1-phenyl-3methyl-5-pyrazolone, acetoacetanilide, and metatolylene-diamine may also be used in the production of excellent colors. In a broader sense the end component is a coupling component consisting of an hydroxy or an amine compound from the benzene, naphthalene, pyrazolone, and aceto-acetarylide classes, which in each instance is free from water-solubilizing groups, such as carboxylic and sulfonic acids.

A HOaS I. The end component may bear the same substituents (except in the coupling position) that may be included in the other nuclei. The symbol M. A. B. means meta-amino-benzoyl, and the symbol P. A. B. means para-amlno-benzoyl.

K. As many apparently widely diflerent embodiments of this invention may be made without departing from the spirit and scope thereof, it is to be understood that I do not limit myself to the specific embodiments thereof except as defined in the appended claims.

I claim:

1. A dyestufl represented by the formula:

NHOCO H N-N on 0H N=N NHOQO 2. A dyestufl represented by the formula:

HOaS

in which X is one of a group consisting of hydrogen, halogen, allgvl, alkoxy, alphyl, carbon, sulfonic acid, aryl' is an aromatic radical from the group consisting of benzene and naphthalene, E is an and component being a radical having a naphathalene, pyrazolone, aceto-acetanilide free fgrom suiionic or carboxylic acid groups.

- 3. A compound having the formula of claim 3 inwhich the endaaogroupsaremetaorparato the CORE groups, in which the amino-naphthol- 1 acid, and in which the diamino-diphenyl-urea is one o! the group consisting oi 3:3 and 4:4- diamino-diphenyl-urea.

4. The process which comprises cellulose with 3:$'-diamino-dlphenvl-urea which a. mW-diainino-aiiphenyI-ureu ,sulfonic m u fi-amino-ii-naphthol- 'l-sulfonic impregnating had been azotized and coupled to two mols of 2(3'-amino-benzoy l-amino) 5-naphthol 7 sultonic acid, rinsing he dyed fabric, azotizlng the color thereon, and coupling with beta-naphthol.

5. The process which comprises a'zotizlng a, compound represented by the formula:

in which X is one of a group consisting of hydrogen, halogen, alkyl, alkoxy, alphyl, carboxy, and sulfonic acid, and coupling it to one of the group of coupling components consisting ot beta-naphthol, l-phenyl-3-methyl-5-pyrazolone, aceto-acetanilide, and meta-tolylene-diamine.

fi (4'-amiuo -benzoyi amino) 5 -naphthol- 7-sulfonic acid beta naphthol in whichmeanu coupled by the diam reaction.

"I. uza'wamino-dlphenyl-ul'eu *2 (42 amino benzoyl amino) E-naphthol- 7-sulfonic acidbeta naphthoi 2 (4'- amino -henzoyi amino) 5-naphthoi- 'Z- sulfonic ucidl-phenyl-3-methyl-5-spyrazolone 2 (4 aminobennoyl-amino) Eli-naphthal- 7-sulfonic acid- 1-phenyl-3-methy1-5-pyrazolone.

SWANIE S. ROSSANDER. 

